Beta-aliphaticaminopropionamides

ABSTRACT

Beta -ALIPHATICAMINOPROPIONAMIDES HAVING A SECONDARY-ALKYL GROUP PREPARED BY THE REACTION OF A SECONDARY-ALKYL AMINE OR DIAMINE WITH ACRYLAMIDE PROVIDING A SUPERIOR PRODUCT FOR USES SUCH AS HOT MELT WAX ADHESIVE SLIP AGENTS AND AS SETTLING AGENTS FOR PARTICULATE SUSPENSIONS IN HYDROCARBON SYSTEMS.

United States Patent Inventors Eugene J. Miller, J r.

Wheaten; Harlan E. Tiefenthal, Western Springs; Steven C. Dueey, Broadview; Frederick S. Marsh, Chicago, all of I11.

Appl. No. 663,520

Filed Aug. 28, 1967 Patented Sept. 21, 1971 Assignee Armour Industrial Chemical Company fi-ALIPHATICAMINOPROPIONAMIDES [56] References Cited UNITED STATES PATENTS 2,523,275 9/1950 Bruce et al 260/562 3,201,472 8/1965 Spivack 260/583 FOREIGN PATENTS 723,006 2/1955 Great Britain 41,213 1966 Japan Primary ExaminerAlex Mazel Assistant ExaminerR. v. Rush Att0rneysCarl C. Batz and Francis W. Young ABSTRACT: B-aliphaticaminopropionamides having a secondary-alkyl group prepared by the reaction of a secondary-alkyl amine or diamine with acrylamide providing a superior product for uses such as hot melt wax adhesive slip agents and as settling agents for particulate suspensions in hydrocarbon systems.

fl-ALIPHATICAMINOPROPIONAMIDES BACKGROUND Prior to this invention, fl-normal-alkyl amino-propionamides have been known. The propionamides of this invention having a secondary-alkyl group attached to the amino nitrogen atom, have been produced from recently available N- secondary-alkyl primary amines and alkylene diamines derived therefrom and have been found to be surprisingly superior to other amides when used as hot melt wax slip agents and for the precipitation of particulate suspensions in hydrocarbon systems.

SUMMARY OF lNVENTlON This invention is directed to ,B-aliphatieamino-propionamides having the formula wherein R is selected from the group consisting of secondaryalkyl and secondary-alkyl-NH(CH ),,-wherein said alkyl radicals have from about 6 to 22 carbon atoms and n is an integer from 2 to 4. One preferred embodiment is directed to compounds of the above formula wherein R is selected from the group consisting of wherein x and y are integers having a sum of about 3 to 19.

The Baliphaticaminopropionamides of this invention may be prepared by the reaction of N-secondary-alkyl amines with acrylamide in accordance with the following reaction:

RNH CH,,=CHCHN RNHCH CH CNH wherein R is defined as in the above formula. The reaction may preferably be carried out by slow addition of an equal molar amount of acrylamide to the amine followed by stirring for a to 60 minute period. The temperature for the reaction should be maintained at from about 40 to 100 C. The product may be filtered through a pressure filter to remove any polyacrylamide present. Very high, almost quantitative, yields of product are obtained by this method.

The secondary-alkyl primary amines used as reactants to form the compounds of this invention may be obtained by hydrolysis of N-secondary-alkyl amides obtained by the amidation of an olefin in the presence of hydrogen fluoride as described in U.S. Pat. application Ser. No. 396,287 filed Sept. 17, 1964 now U.S. Pat. 3,338,967 issued Aug. 29, 1967. N- sccondary-alkyl alkylene diamine compounds suitable as reactants to produce the novel compounds of this invention may be obtained from secondary-alkyl primary amines as described in U.S. Pat. application Ser. No. 422,504, filed Dec. 31, 1964 now U.S. Pat. No. 3,398,196 issued Aug. 20, 1968.

The novel aminopropionamides of this invention, as illustrated by the above formula, reflect the isomeric nature of the amine reactants as used for their preparation, The amine reactants used to prepare the aminopropionamides compound of this invention may be derived from olefinic compounds, in which'case the nitrogen atom attached to the secondary-alkyl group may be attached to different interior carbon atoms along a hydrocarbon chain. lsomeric mixtures of various secondary-alkyl amines may be used to form the novel aminopropionamides of this invention. Of particular importance as reactants of this invention are secondary-alkyl amine compounds derived from alpha olefins. Further, the secondary-alkyl amine reactants used to form the aminopropionamides of this invention may consist of a mixture of different hydrocarbon chain lengths, usually extending over a range from 2 to about 6 numerically consecutive chain lengths. The mixture of chain lengths is generally dependent upon the cut of mixed olefins from which the secondary-alkylamines were derived, and is not critical in the formation of the compounds of this invention.

One phase of our invention relates to the surprising effectiveness of the branched chain B-aliphatic-aminopropconamides as slip agents in hot melt wax adhesive compositions. A large use of such adhesives is to bond layers of paperboard to one another. Adhesive is generally applied to the paperboard by steel rollers which are submersed in a heated vat containing the wax adhesive and then brought into contact with the paperboard. The slip agent is used to prevent the wax adhesive from sticking to the roller as it is being applied to the paperboard. It is desirable that the slip agent have no deleterious effect on the bonding of the adhesive wax coated layers of paperboard to each other, but should prevent the adhesive from adhering to the steel roller. It has been found that the compounds of this invention function for use as hot melt wax slip agents in a manner superior to oleylamidc which is presently being used for such purposes, and further, it has been found that the branched chain propionamides of this invention are surprisingly superior to the normal-alkyl propionamides. The compounds of this invention are added to the hot melt wax adhesive in an amount from about 1 to 10 weight percent. It is preferred to utilize from 2 to 6 weight percent of the propionamide compounds of this invention. THE BRANCHED Cl-lAlN fl-aliphaticaminopropionamides may advantageously be used with other additives, and it has been found particularly advantageous to blend the compounds of this invention with fatty acids, especially phenylstearic acid.

The following examples are presented to illustrate the present invention.

EXAMPLE] B(C-,C sec-alky1amino)propionamide was prepared in the following manner. A 100 ml. round bottom flask with a magnetic stirrer was charged with 0.3 mole of C C secondary-alkyl primary amine. The temperature was raised to C. and 0.3 mole of acrylamide was added slowly over a 25 minute period. The mixture was stirred at 80-95 C. for 30 minutes. The crude product was obtained as a pale yellow oil (92.5 percent yield) having the following analysis:

Neutralization equivalent 202 (calcd. 205) Primary amine 16.7 percent Secondary amine 76 percent EXAMPLE ll B-(C C sec-alkylamino) propionamide was prepared following the procedure of Example I except that C,,C secondary-alkyl primary amine was used. The mixture was stirred at 8090 C. for 30 minutes. The crude product was obtained as a yellow oil in almost quantitative yield having the following analysis:

Neutralization equivalent 232 (calcd. 233) Primary amine 12.2 percent Secondary amine 83.5 percent EXAMPLE lll B(C C sec-alkylamino)propionamide was prepared following the procedure of Example I using 0.3 mole of C -C secondary-alkyl primary amine. The temperature was raised to 90 C. and 0.33 mole of acrylamide was added over a 15 minute period. The mixture was stirred at 95 C. for 1 hour, then filtered through a pressure filter to remove any polycrylamide. The crude product was obtained as a yellow oil, 94.5 percent yield, having the following analysis:

Neutralization equivalent 267 (calcd 264) Primary amine 14.9 percent Secondary amine 78.0 percent EXAMPLE lV ,B(C, C sec-alkylamino)propionamide was prepared as in Example I using 0.2 mole of C -C seeondary-alkylamine and 0.2 mole of acrylamide to obtain a crude product having the appearance of a yellow oil in almost quantitative yield and having the following analysis:

Neutralization equivalent 357 (calcd 358) Primary amine 13.2 percent Secondary amine 83.5 percent EXAMPLE V 3[3'(C -C sec-alkylamino)propylamino]p ropionamide was prepared following the procedure of Example I using 0.2 mole of N-(C -Ch sec-alkyl)-l ,3- propanediamine and 0.2 mole of acrylamide. The crude product was obtained in almost quantitative yield and has the following analysis:

Neutralization equivalent 129 (calcd l3l Primary amine 5.7 percent Secondary amine 93 percent EXAMPLE Vl EXAMPLE Vll 3[3(C,,-C sec-alkylamino)propylamino]propionamide was prepared using the apparatus described in Example I. 0.2 mole of N(C C sec-alkyl)l 3propanediamine was added to the flask, the temperature was raised to 85-95 C. and 0.2 mole acrylamide was added slowly over a 15 minute period. The mixture was stirred for 1 hour at 95-l 10 C. and then filtered to remove any polyacrylamide. The crude product was obtained in 95.5 percent yield as a yellow oil having the following analysis:

Neutralization equivalent l63 (calcd. 162.5)

Primary amine 6.35 percent Secondary amine 81.2 percent Tertiary amine l 1.9 percent EXAMPLE VIII 3[ 3 '-(C, -C sec-alkylamino)propylamino]propionamide was obtained by following the procedure of Example I using 0.2 mole of N(C C sec-alkyl)-l, 3-propancdiamine. The crude product was obtained in almost quantitative yield and has the following analysis:

Neutralization equivalent 205 (calcd. 203) Primary amine 8.2 percent Secondary amine 90.5 percent EXAMPLE lX Branched chain fialiphaticaminopropionamides of this invention were compared with straight chain llaliphalieaminopropionamides for the settling of fuel oil sludge from kerosene. Amounts of additives as set forth in Table l were added in a 1 percent kerosene stock solution to I00 mls. of kerosene. Then 5 gms. of fuel oil sludge and I0 mls. of tap water were added to the bottles containing kerosene-additive mixtures and the bottles were then shaken vigorously. The bottles were then allowed to stand without any movement and the time for the sludge to settle out was observed and recorded. A control containing no additive was run under the same conditions. The results are shown in Table l.

TABLE 1 Time for Particles to Chemical Additive p.p.m. Settle Out ControlNo additive 72 hours fl-(C -C .rec-alkylaminol0 3-5 min. propionamide 25 3-5 min. 50 3-5 min.

100 3-5 min.

B-(cncoamino) propionamide l0 3 hours 25 3 hours 50 4 hours 100 4 hours 3[3'-tC C .rec-alkylamino) l0 15 min. -propylamino] propionamide 25 I5 min.

3-[3'-(cocoamino) propylamino] l0 5 hours 25 2 hours -propionamide "Cocoamines are derived from coconut oil fatty acids having hydrocarbon chain lengths of from G -C saturated and unsaturated, predominately dodecyl and tctradecyl.

EXAMPLE X The use of compounds of this invention and other amides as slip agents for hot melt wax adhesives were compared in the following manner. The noted slip agent was added in the below stated quantity to a melted adhesive containing petroleum wax and a copolymer of ethylene and vinyl acetate sold by DuPont under the trademark Elvax. The adhesive containing the slip agent was applied to a strip of cardboard which was then placed with the adhesive adjacent to a sheet of stainless steel and oven cured at 350 for 30 minutes. The stainless steel-adhesive-cardboard sandwich was then placed in an oven at 100 F for an additional 15 minutes. The stainless steel-adhesive-cardboard sandwich was removed from the oven and the ease of stripping the cardboard from the stainless was noted. It is desirable for the cardboard to be readily stripped from the steel.

Two pieces of cardboard coated with the same adhesive containing slip agent were placed with adhesive sides adjacent and oven cured at 300 F. for 20 minutes. The steel-adhesivecardboard sandwich was cooled for 4 hours. It was then attempted to strip the two pieces of cardboard apart and the results are noted below. It is desirable that the two pieces of cardboard be inseparable.

5 percent oleylamide, which is used as a slip agent in hot adhesive waxes, was used as a standard. The results are shown in Table II.

EXAMPLE X! The same procedureas described in Example X was followed using the following hot melt was adhesive:

percent pure refined paraflin wax (sold by the Texas Company under the trademark Texwax) l0 percent polybutylenc l0 percent crude polystyrene The noted slip agent was added in the below stated quantities to the melted adhesive which was then applied to the paperboard and was subjected to the same treatment and conditions as set forth in Example X, giving results shown in Table III using the same rating scale as in Table ll.

TABLE II Steel to Cardboard to Cone, cardboard, cardboard at Slip agent additive percent 100 room temp.

Olcylnniidc 5 0 +3 +1 MO -C sec-alkyl)aminopropionamide 4 +2 +2 3 +1 +2 11- L( 1 C sec-alkyl)aminopropionamide 2 lhonylstearic acid 22/; +5 +2 {a-(C 1 -09 sec-alkyl) amlnopropionamide. 2 l'lienylstearic acid 2 +5 +1 :3-4' 42 see-alkyl)aniinopropionamiden 1% liu-nylstcurlc acid 1% +2 +2 Nora-Ease 0t stripping: 05% oleylamide; +1, +2, +3, and +4str1pped more easily TABLE III Steel to Cardboard to Cone, cardboard, Cardboard at Slip agent additive Percent 100 F room temp.

Olcylamide 5 0 0 fi-(O leylarnino) propionamide. 5 +1 0 3-l3-(oleylamino)propylamino prop na 5 +1 0 3-[3"(oleylamino)propylamino propionamide. 256 +2 +1 Phenylstearic acid 2% 3-[3'-(C C seo-alkylamino)propylamino propionamide 5 +3 +1 3-l3-(C15-C sec-alkylamino)propylamino propionamide.. 2% Phcnylstcaric acid 295 +5 +2 'Oleylamino is derived from commercial olcic acids having hydrocarhoh chain lengths from C C saturated and unsaturated, predominately olcic.

We claim: 1 A fl-aliphaticaminopropionamide having the formula.

wherein x and y are integers having a sum of 3 to l9.

3. A compounds of claim 1 wherein R is selected from the group consisting of CHS((IJH2)X l ormcHo wherein x and y are integers having a sum of 3 to 19.

4. A compounds of claim 3 wherein x and y are integers hav ing asum from 8 to 11.

5. B-aliphaticaminopropionamide having the formula wherein x and y are integers having a sum of 3 to 1 9.

6. A compounds of claim 5 wherein it and y are integers havingasum from 8 to ll. 

2. A compounds of claim 1 wherein R is selected from the group consisting of wherein x and y are integers having a sum of 3 to
 19. 3. A compounds of claim 1 wherein R is selected from the group consisting of wherein x and y are integers having a sum of 3 to
 19. 4. A compounds of claim 3 wherein x and y are integers having a sum from 8 to
 11. 5. Beta -aliphaticaminopropionamide having the formula wherein x and y are integers having a sum of 3 to
 19. 6. A compounds of claim 5 wherein x and y are integers having a sum from 8 to
 11. 